Durable "Green" Concrete from Activated Pozzolan Cement

James Hicks, P.E. CeraTech, Inc., 3501 Brehms Lane, Suite D, Baltimore, MD 21213, (936) 697-2893, FAX (443) 524-4411, email: jim.hicks@ceratechinc.com

Abstract Concrete is the most widely used man-made material, and the manufacture of portland

cement - the active ingredient of concrete - accounts for 6 to 8 percent worldwide of all anthropogenic emissions of carbon dioxide, a leading greenhouse gas involved in global warming. Globally, nearly 2.77 billion metric tons (t) (3.05 billion st) of portland and hydraulic cement was produced in 2007. The concrete construction sector has a responsibility to take immediate action to reduce its environmental impacts, including the generation reduction of CO2. This responsibility also brings the opportunity to develop innovative technologies, including use of materials from Coal Combustion Products (CCPs).

These newly developed activated fly ash based products leave virtually no carbon footprint. Updated cementitious binder technology eliminates approximately 0.9 t (1 st) of CO2 emitted into the atmosphere per ton of portland cement produced. These cements have been engineered for use in fast track concrete repairs and construction, conventional paving, walls and concrete block masonry, new construction and repair projects. Activated pozzolanic material cements and resulting products are comprised of up to 95 percent green sustainable industrial waste stream materials, primarily fly ash. They are manufactured via a low energy, powder blending process. Key to green cement development was creating a material matrix that has a very dense crystal structure. This green cement technology possesses excellent performance and durability characteristics, including high early strengths and 28-day strengths over 70 MPa (10,000 psi). Moreover, they can be placed effectively with ambient temperatures ranging from -1C to 49C (30F to 120F).

1. Introduction 2. Coal is a relatively abundant, reliable and inexpensive energy source for worldwide power generation. However, it is also one of the main producers of Carbon Dioxide (CO2). Fossil-fuel combustion in power plants, vehicles and heaters around the planet released 31.5 billion t (34.7 billion st) of the greenhouse gas (Bloomberg, 2009). The U.S. alone produces approximately 1.5 billion tons of CO2 annually from all sources; globally, coal is attributed to one third of all CO2 emissions (USEPA, 2009). Coal when used as a fuel, is also one of the main producers of Carbon Dioxide (CO2). Coal combustion has been brought into question regarding other noxious waste products like Mercury, Nitrogen Oxide and Sulphur Dioxide. Economically and technically, viable mitigation technologies exist for the above mentioned pollutants with the exception of CO2 (Hicks, et. al. 2009). Another large producer of CO2 emissions is portland cement kilns. For instance, the use of fly ash (a by-product of coal burning in power generation and most common CCP) in the cement-making process could reduce substantial amounts of CO2 emitted by a cement kiln. Worldwide, the production of portland cement alone accounts for 6 to 8 percent of all human generated CO2 greenhouse gases (Huntzinger, Deborah N. and Eatmon, Thomas D., 2009). Portland cement production is not only a source of combustion-related CO2 emissions, but it is also one of the largest sources of industrial process-related emissions in the United States. Combustion related emissions from the U.S. [portland] cement industry were estimated at approximately 36 Tg of CO2 accounting for approximately 3.7 percent of combustion-related emissions in the U.S. industrial sector in 2001 (USGS, 2002) In 2007, a survey of 161 US coal-fired power plants (out of 500 operating coal fired power plants) showed production of 118 million t (131 million st) of CCPs. Of this amount, only 12.4 million t (13.7 million st) were used in concrete or as a concrete product. The survey reported that more than 45.4 million t (50 million st) of fly ash is still being disposed of in US landfills annually. (ACAA, 2008) Clearly, the use of otherwise waste materials for beneficial use can reduce the need for more landfills and the amount of CO2 produced. Extensive research is underway to find more economically feasible alternatives for carbon dioxide capture and storage (CCS). However, until financially and environmentally sustainable alternatives are in use, the toxic byproducts of pulverized coal-based power generation (conventional) will be an issue for decades to come. A successful CO2 mitigation process presently lies in private-public strategy that combines existing power plants (revamped to capture, geologically store and/or
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enhance oil recovery), and new ones using more advanced coal power generation technologies like the Integrated Coal Gasification Combined Cycle (IGCC). These approaches alongside proactive regulation could build a relatively sustainable alternative for the future (Floris, Vinio, 2009). Not all current power plants will be refurbished as mentioned above; yet CCPs from plants that do not convert to CCS technologies could still be put to good use through innovative ways in order to assist in the decrease of greenhouse gases. For instance, fly ash (a by-product that largely ends up in landfills) can substitute for portland cement and improve structural changes to the end product (concrete and others). The use of one unit of fly ash reduces approximately one unit of CO2 emitted by a cement kiln. Fly ash and other CCPs in the cement-making process could also avoid the use of the high energy requirement and significantly reduce the volume of useable material taken to waste management sites (Floris, Vinio and Hicks James K., 2009). Governments and corporations are beginning to see the benefits of using CCPs for mitigating greenhouse emissions. For instance, in the State of California California Assembly Bill 32 (AB 32) was signed into law in 2006. AB 32 is seeking reductions in greenhouse gas emissions from the production of portland cement, primarily carbon dioxide. The California Air Resources Board has already passed regulations requiring annual reporting of greenhouse gases-related emissions data from portland cement manufacturing plants. California expects a potential 1.1 million tons reduction in CO2 emissions by 2020 from cement manufacturing (with a 9% reduction by 2011) and a potential 0.54 to 1.6 million t (0.6 to 1.8 million st) reduction in CO2 emissions by 2020 from concrete manufacturing (with 9 percent to 27 percent replacement of portland cement with CCPs). By 2050 an 80 percent reduction in greenhouse gas emissions below 1990 levels is targeted. (www.arb.ca.gov/climatechange). Fly ash can be used as a component in the manufacture of cement while improving the end products of concrete, mortars and grouts (NRMCA and PCA, 2006). Use of fly ash allows their durability factors to be substantially improved. Although fly ash is a very good substitute for cement when used as a pozzolan in portland cement concrete and other cementitious products, importantly, fly ash can be used in very high quantities with activated fly ash cements. These cements have been engineered for use in conventional paving, walls and concrete block masonry, new construction and repair projects.

3.

Coal-based Power Generation

Around the world, coal is primarily used as a solid fuel to produce electricity and heat through combustion. Globally, 25% of total energy sources come from coal while in the US it is about 50%. Approximately, 82 percent of coal reserves (data of 2008) were concentrated in six countries (in descending order: USA, Russia, China, India, Australia, and South Africa). The US has 29% of the reserves, 216,189 million t (238,308 million st), while Russia and China hold 19% and 14%, respectively.
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The US produced 20% of the worlds total in 2008 while China and India produced 2.8 billion and 512 million tons, respectively. China is currently the largest producer of mined coal (41% of the worlds total). (British Petroleum, 2009) Global coal consumption is projected to jump nearly 50% by 2030. On a tonnage basis, world coal consumption is projected to grow 47% from 6,117 Mt in 2006 to 8,995 Mt in 2030, an average annual growth rate of 1.6%. The dramatic increase in global use of coal is the result of a predicted 44% jump in world energy consumption (2006-2030). 73% of that projected increase in world energy consumption is the result of expected strong economic growth in non-Organization for Economic Co-operation and Development (OECD) countries. Despite the current near-term economic slump, EIA expects demand for energy for manufacturing and consumer products to rebound after 2010. EIA anticipates a 15% growth rate in OECD countries during the same period. (EIA, 2009) Coal prices have significantly risen since the 1980s after decades of steady pricing. Appendix Figure 1 shows coal prices (US$/st) for Northwest Europe, Central Appalachian US and Japan. US prices were about US $70/st in early 2009. Coal is, compared to other energy sources, the least expensive commodity for power generation. (ACAA Fact Sheet) In 2006, there were 1,493 coal-powered units at electrical utilities across the US with a total nominal capacity of 335.8 GW The US average generated annual power from coal (in 2006) was 227.1 GW. In 2006, China produced 195 GW and it is estimated that it has currently surpassed the US (USEPA, 2006). Without any global climate policies, it is expected that coal production (mainly driven by Australia, China, Russia, Ukraine, Kazakhstan and South Africa) and consumption may increase 30 to 50% by year 2025 (from 2007 data) (US Energy Information Administration, 2009). Until more economically feasible alternatives are developed for capturing and sequestering CO2, conventional coal-based power generation will continue for decades to come. New electric power production technologies and a resurgence in nuclear power electric likely will begin to effect the reductions in CO2 emissions.
4.

Problems, U. Environmental Protection Agency (EPA) and Fly Ash

In 1980, Congress charged the EPA to prepare a detailed study of the health and environmental impact of coal ash. The report was presented in Year 2000 and after discussion at different levels EPA determined that it did not warrant regulations as a hazardous waste under the provisions of the Resource Conservation Recovery Act. After studying coal-fired utility wastes in 1993, the EPA decided to permanently exclude large volume coal fired utility wastes, including fly ash, bottom ash, boiler slag and flue gas emission control waste from the definition of hazardous waste. Studies have shown that although trace elements may leach from coal ash in prolonged contact
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with the water table, they do not migrate far from the ash site and are present in very low concentrations, and therefore do not present a health threat. The 2008, a large Kingston, Tennessee TVA coal combustion residue containment structure collapse opened the discussion considering the amounts of arsenic, lead, barium, chromium and manganese found on that pond (Schlesinger, 2009). However, the ranges of major elements in coal fly ash and soils have been evaluated and are available in National Bureau of Standards Certificate of Analysis (Standard Reference Material 1633a, January 5, 1985). The comparison shows that the constituents in coal fly ash fall within the typical ranges of those in soils found across the U.S. Furthermore, fly ash is commonly used as an additive to concrete building products, not significantly different from that of more conventional concrete additives or other building materials such as granite and red brick. CCP are considered a waste product for power generation facilities. Waste material, however, should be removed and land filled appropriately. The authors have witnessed well-run facilities that do not pose any threats to health and the environment. Stringent regulations likely will move in that direction, but should not to the point to make the product a hazardous material. Such an outcome would seriously affect (and most likely end) the cement/concrete, road base and gypsum board industry that is providing a significant benefit to the environment. Even so, utilizing the fly ash in a positive manner such an blending to become hydraulic cement utilizes those otherwise discarded materials. 5. Cement and Concrete

Concrete is the most widely used man-made material in the world. In 2008 nearly 2.6 billion t (3 billion st) of portland and hydraulic cement was produced worldwide (PCA, 2009). Cement production generates carbon-dioxide emissions because it requires fossil fuels to heat the powdered mixture of limestone, clay, ferrous and siliceous materials to temperatures of 1,500C (2700F). Limestone (Calcium Carbonate - CaCO3) is the principle ingredient of cement. During the portland cement clinker calcining process, CaCO3 is changed to CaO. This conversion releases one mole of CO2 (carbon dioxide) for every mole of CaCO3 consumed in the production process. Approximately one ton of CO2 is released in the production of one ton of portland cement. In the United States, portland cement production alone constitutes about 2-3 percent of CO2 gasses generated annually. Given the impact that portland cement production has on the environment, it is incumbent on concrete manufacturers to actively pursue immediate programs and/or practices that reduce the generation of CO2 emissions. The concrete industry shouldnt consider this obligation a negative, however, because this responsibility also brings the opportunity to develop innovative technological advances in both material and a production processes. Portland cement has long been used in standard building materials. Over the years, various modifiers have been developed for cement formulations to provide particular properties or advantages, such as more rapid curing, compatibility with and resistance to certain materials, and varying strengths, etc. In the past, at times the modified formulations have worked at cross purposes, so that a cement formulation that initially
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cures more rapidly results in a final product with a lower ultimate strength, while the higher late strength portland cement formulations frequently cannot be demolded for substantial periods of time because there is not sufficient early strength. Over the past thirty years, scientists have pursued various methods to produce a class of fly ash based cement known as geo-polymers. These early precursors to present products were found - even though mineral in composition - to provide many of the properties of molding resins, such as epoxies and polyurethanes. Some geopolymeric cementitious products are in used still today in various parts of the world. Such geopolymers are described and claimed, for example, US Patents. (Davidovits, 1982). These geo-polymers are primarily composed of silicas and aluminas, mixed and reacted in particular ways to provide the desired structure. While, in general, these geopolymers are perfectly adequate for the purposes intended, as such, they do not always provide the types of strengths sought in a concrete composition. Furthermore, geopolymers typically require post reaction thermal processing for up to 24 hours in order to achieve desirable strengths. Below is a recent historical summary of earlier versions of pozzolan based cements:
Alkali activation of solid, non-portland cement precursors (usually high-

calcium slags) was first demonstrated in reasonably modern times by Purdon in 1940, and was developed on a larger scale primarily in Eastern Europe in the succeeding decades, (vanDeventer, Jannie S.J. et. al, 2010) 1970s: Geo-polymers from fly ash, cements high in Al-Si. J. Davidovits makes references to their use in historical construction techniques. 1980s: Activated fly ashes blended with cement, e.g. mostly two step mixes unconditionally require addition of the activator at the jobsite.
1990s through mid-decade beginning in 2000: development of one step mixes,

activator in product package or cement. The cementitious compositions typically consisted of harsh acids and bases such as citric acids (pH~2.2) and alkali metal activators including alkali hydroxides (pH~12-14) and metal carbonates (pH~11.6). These included patents by Gravitt, Kirkpatrick, Styron, Hicks and others. There were some drawbacks to these materials. The prior art required acid -base reactions. These reactions sometimes were non-uniform and difficult to control. The art has needed and continued to seek a hydraulic cement composition, which provides for utilization in standard situations, while providing both a high early strength and an ultimate, very high strength. In particular, compositions having a minimum strength of 28 MPa (4,000 psi) at 4 hours, the release strength necessary for prestress work, have been sought.

1970s: Geo-polymers from fly ash, cements high in Al-Si. J. Davidovits makes references to their use in historical construction techniques.
1980s: Activated fly ashes blended with cement, e.g. mostly two step mixes

unconditionally require addition of the activator at the jobsite.

6.

The New Generation of Cement Technology

This new generation of fly ash based cements offers the user a unique set of mechanical and dimensional properties competitive in cost to current cementitious product offerings, providing the user with a value added alternative solution for todays most challenging construction cementitious repair, product and paving applications. The technology is built around a highly flexible chemistry that allows for the inclusion of a wide array of waste materials as part of its binder matrix, establishing it as a truly green sustainable construction material with unique performance and application advantages. This new green cement technology is based upon an all fly ash cement design that requires no portland cement in its matrix. Through a detailed study of various types of chemistry and reactive fly ash-based cement pastes, key aspects of the mineralogy have been identified for determining the usefulness of various fly ash sources as high performance cements, including non acid-alkali activated cements. Key to green cement development was creating a material matrix that had a very dense crystal structure eliminating the movement of water and other chemicals through the material matrix; water being the catalyst for many of the reactions that occur in the concrete matrix. This is accomplished through the simultaneous dissolution and retardation of the Calcium Oxide phase to solubilize both the silicate and aluminate amorphous phases. The minerals recombine to the desired structure providing desired mechanical and dimensional properties. Thusly, pozzolanic materials are modified with chemicals to produce the desired structure. This is denoted by the phase diagram in accompanying Figure 7. At the corners of the diagram are the key minerals that are found in typical cements. The red-hatched zone in the upper half of the diagram represents what is theorized to be the perfect cement. It characterized by a very dense crystal structure exhibiting the optimum chemical ratio of calcium to silicates to aluminates. The micro pore structure is very small, greatly limiting the movement of liquids within
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the material matrix. The crystal structure of portland cement is dominated by Tricalcium Silicate (C3S) and Dicalcium Silicate (C2S) components producing a crystal structure that is not as dense leading to relatively a large voids structure within the material matrix. The chemical and mineralogical improvements, coupled with the much higher fineness of pozzolan based cements ground leads to much lower porosity in the concrete. The lower porosity provides for very low water to cementitious ratios and improved durability factors. Having developed a technique to fingerprint raw materials as well as a road map of good fly ash sources, the new approach is able to maintain quality assurance on product lines using a broad array of fly ash sources, and blends of sources. The improved activated hydraulic cement technology is the principal backbone chemistry for a range of product offerings from small area repair packaged goods to new construction concretes. Products from the non acid-alkali activated cements were developed specifically to satisfy user or application performance requirements. Each product is water mixed, single component activated, turnkey concrete, mortar or grout with flexible working times from 15 minutes to three hours. The products were engineered to allow for mixing, hauling, placing and finishing using standard industry equipment and practices. The products were designed for applications where speed, strength and durability were desirable performance characteristics. Compressive strengths of more than 17 MPa (2,500 psi) in as little as 60 minutes supported by bond strengths of over 21 MPa (3,000 psi) and flexural strengths over 10 MPa (1,500 psi) in 7 days frame the technologys mechanical properties. Dimensional stability is highlighted by shrinkage of less than 0.04% length change in 28 days. Principle benefits of this new class of products include: Non-shrink. Exceptional sustained bond strengths (slant shear and direct tension). Low coefficient of thermal expansion. Modulus of elasticity consistent with Portland cement concrete. Low permeability. High resistance to freezing and thawing. High resistance to scaling. High resistance to sulfate and chemical attack. Exceptional durability. Placement temperature tolerant. No epoxy resins are contained.

Specific areas of products developed meeting objective criteria fall into several areas:

Rapid Repair Ready Mix including paving Volumetric mixer concrete and mortar
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Concrete block/grout/mortar Precast High Temperature Resistant Materials. Chemical Resistant Materials

Some of the more specific examples descriptions are:

Rapid repair products all have cementitious components greater than 90 percent coal ash, and contain no portland cement. Based upon the size of the repair, products range in working time from 15 to 45 minutes, offering return to service ranging from 1 to 4 hours (See Table 1). All products can be mixed with conventional mixing equipment and placed like portland cement products, however without the requirement of bond coats. Ready-mix truck delivery. For large placements such as roadway slabs, ash-based pozzolanic cements have been adapted to ready-mix batch plant/transit truck mixing and placement. These products are able to be site activated (up to 4 hours transit time), and adjusted to placement times from 1 to 3 hours. Return to service can be achieved in as little as 6 to 12 hours (See Table 2). Slump control can be adjusted to range from roller-compacted concrete (RCC) to a self-consolidating concrete (SCC). Volumetric mobile mixer use. The volumetric pozzolanic product utilizes the same backbone chemistry as the rapid repair products. For larger placements that also require fast return to service, the pozzolans have been adapted to work in a volumetric mixer, allowing from 20 to 50 minutes of placement time, with return to service in as little as 1 hour depending upon the user requirements. With DOT and DOD applications, the principal benefit of volumetric placement is the ability to place larger volumes while still taking advantage of the quick return to service. One version of this product can be used as a flowable grout capable of providing up to three hours of working time, yet providing up to 35 MPa (5000 psi) in compressive strength in 24 hours.

Among the general construction and precast benefits are: For vertical construction markets, including columns, flooring, and tilt-up construction, ash-based pozzolanic cements have been adapted to perform as selfconsolidating concrete (SCC). These products permit easy pumping and long working times, yet can suspend aggregate, provide sufficient placement time, and offer early return to service. These are placed with a conventional batching and mixer system. Precast. Additional benefits of non acid-alkali activated ash-based pozzolanic
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cements also extend to precast concrete applications. Higher strength precast components can be developed, offering the ability to strip molds much earlier than with cement based concrete. This ability permits faster turn-around and throughput to the manufacturer. High Temperature Resistant Materials. A unique benefit of ash-based pozzolanic cements is their high temperature resistance capabilities. Ash-based cements are naturally refractory given their amorphous glass chemistry. Coupled with other high-temperature admixtures, these products are the only materials that have passed Mach 1 shock testing at 1700F (927 C) for 300 cycles. This result has qualified the material for use as a run-up and takeoff pad for current emerging vertical takeoff aircraft (VTOL) including the AV-8, V-22 Osprey, and the new Joint Strike Fighter. Armor and Protective Materials. Non acid-alkali activated fly ash-based pozzolanic cements are not only able to achieve high-early strength, but very high strengths overall. In one development area, a class of cements has been developed capable of achieving over 69 MPa (10,000) psi in 24 hours, and up to 152 MPa (22,000 psi) within 28 days. These products are in development with the US Army Corps of Engineers as a field emplaced armor material capable of withstanding both blast and fragment penetration. Concrete block/grout/mortar. The non acid-alkali activated fly-ash based pozzolanic cements have also been optimized to product both normal strength and high strength concrete masonry units (CMUs). Products have been able to achieve strengths ranging from 14 to 69 MPa (2,000 to 10,000 psi) using conventional concrete block manufacturing facilities, techniques, and cement percentages equal to those used by conventional cement. 7. Conclusions

Despite all global warming concerns and being in the midst of a financial crisis, an approximate growth of 30-50 percent of coal power generation is expected between Years 2007 to 2025. The installed capacity would jump to approximately 2.1 million MW. Initial estimates were even higher but the US and Europe are scaling back due to strong environmental pressures. China alone would add approximately 350,000 MW during this period while India would follow with more than 100,000 MW. As it was examined in Sections 2, 3 and 4, it is essential to emphasize that the use of CCP could make key reductions in CO2 emissions by using byproducts to make cement, substituting for portland cement in concrete, and reducing energy given the energy-efficient nature of concrete structures. It is important to point out that the CCP option is only available for pulverized coal plants. IGCC units follow a different technique and do not produce any cementitious materials as by-products. These cutting-edge, next-generation green non acid-alkali activated fly-ash based pozzolanic cements provide the construction a value added alternative to traditional cement product offers. The extent of engineering that has been done with the product offers widest range of end-use applications from any pozzolan, removing it from its previous limited use as a short-life rapid repair product only. Moreover, the amount of research that has been conducted on understanding fly-ash chemistry and mineralogy
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has extended the ability to use a much wider range of high calcium coal ash while maintaining predictable product performance. These truly green building materials are comprised largely of renewable, recyclable or reusable resources. They are the only cements in the world whose chemical matrix is comprised of more than 95% waste materials. See Figure 5. This new generation of all ash-based pozzolanic cements also furthers the ability to utilize green building technology for the widest range of end-use markets, including most DOT, DOD, and building construction market applications while meeting International Building Code and ASTM Standards. It is important to note that although the environmental and even economic benefits from using CCPs are apparent, they are still underutilized. The American Coal Ash Association reported that less than 40 percent of CCP are used. The Association only reports affiliated utilities. The authors estimate that less than those amounts are currently used and end up in landfills, creating a burden to the environment and the economy of different enterprises. We all need to understand that we must adopt sustainable energy policies to avoid endangering energy security and control carbon emissions. Without any intervention, CO2 could increase 42.4 Gigatons in 2035 from 29.7 in 2007 (EIA, 2010). This increase is a real and immense challenge that has to be managed promptly.
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KEYWORDS: Recycled, cement, green, concrete, CO2 reduction, CCP, Sustainable

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8. References

13

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promptly.

Figure 4. 1996-2007 CCP Beneficial Use versus production. Source: American Coal Ash Association.

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References American Coal Ash Association. 2005. ACAA Fly Ash basics Quick Reference Card. American Coal Ash Association. Coal Combustion Products: Not a Hazardous Waste. British Petroleum. 2009. BP Statistical Review of World Energy.

Floris, Vinio, Hicks James K., 2009. Environmental Benefits of Coal Combustion Products, Pittsburgh, Coal Conference. Floris, Vinio. 2009. Challenges and Achievements of Coal-Based Power Generation: Moving Towards a Holistic and Sustainable Approach. Proceedings of the International Association of Energy Economics, Santiago, Chile. Hicks, James K., Mike Riley, Glenn Schumacher, Raj Patel and Paul Sampson. 2009. Utilization of Recovered Materials for High Quality Cements and Products. Massachusetts Institute of Technology. 2007. The future of Coal.
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Schlesinger, Richard. April/March 2009. Coal Ash Piles Up. Energybiz. US Energy Information Administration. 2007. US Coal Supply and Demand, 2007 Review.

US Environmental Protection Agency. 2008. Inventory of U.S. Greenhouse Gas Emissions and Sinks: 1990-2006, Report No. 430-R-08-005.

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World CO2-Emissions Growth Keeps Focus on Coal, Bloomberg Business Week, June 10, 2009 United States Environmental Protection Agency (USEPA), Recent Trends in U.S. Greenhouse Gas, Climate Change, Emissions, 2010 Inventory of Greenhouse Gas Emissions and Sinks, www.epa.gov/climatechange/emissions British Petroleum, BP Statistical Review of World Energy, (2009) EIA International Energy Outlook, EIA predicts surge in world coal consumption, www.immining.com/2009/06/07/eia-predicts-surge-in-world-coal-consumption/2009 American Coal Ash Association (ACAA), 2007 Fly Ash Survey, (2008) Hicks, James K., Mike Riley, Glenn Schumacher, Raj Patel and Paul Sampson, Utilization of Recovered Materials for High Quality Cements and Products, World of Coal Ash, University of Kentucky Center for Applied Energy Research, Lexington, KY, 2009. Van Ost, Hendrik G, United States Geological Survey, Cement, 2002 Huntzinger, Deborah N and Eatmon, Thomas D., Journal of Cleaner Production, Elsevier, (2009) 668 675 Floris, Vinio, Challenges and Achievements of Coal-Based Power Generation: Moving Towards a Holistic and Sustainable Approach. Proceedings of the International Association of Energy Economics, Santiago, Chile (2009). Floris, Vinio, Hicks James K., Environmental Benefits of Coal Combustion Products, Pittsburgh Coal Conference, University of Pittsburg, PA (2009). California Environmental Protection Agency, Air Resources Board, www.arb.ca.gov/climatechange (2010) Ready Mixed Concrete (RMC) Research Foundation and the Portland Cement Association (PCA), The Ready Mixed Concrete Industry LEED Reference Guide, nrmca.org/greenconcrete/LEEDreference guide (2009) US Coal Supply and Demand, 2007 Review, www.eia.doe.gov.coal, 2007 US Environmental Protection Agency. 2008. Inventory of U.S. Greenhouse Gas Emissions and Sinks: 1990-2006, Report No. 430-R-08-005, www.epa.gov/climatechange/emissions/usgginventory.html US Energy Information Administration. www.eia.doe.gov 2007 Schlesinger, Richard. Energybiz, Coal Ash Piles Up (April/March 2009) Portland Cement Association (PCA), Economic Research, Market Data Reports, www.cement.org (2009) Davidovits, Joseph, United States Patent Office (USPTO), U.S. Pat. Nos. 4,349,386 (1982) and 4,472,199 (1984), www.USPTO.gov van Deventer, Jannie S.J., et. al, The role of research in the commercial development of geopolymer concrete, International Cement Microscopy Association, March 2010 Conference, www.cemmicro.org U. S. Energy Information Administration, 2010 CO2 Forecast Highlights, www.eia.doe.gov/international (2010)

LIST OF TABLES AND FIGURES Figure 1. Price changes of coal in different regions of the world. Figure 2. 2006 US sources of CO2 emissions. Figure 3. 1996-2007 CCP Beneficial Use versus production. Figure 4. World net Electricity generation by fuel, 2007-2035
Figure 5. Construction of base for a heat treating facility in Houston, Texas. Figure 6. Micrograph of CSH Formation in Activated Fly Ash Cement. Figure 7. CeraTech Cement design. Figure 8. Marine Corps Concrete Installation

Table 1. Performance characteristics of an activated pozzolan based cement repair material Table 2. Characteristics of an activated pozzolan cement fast return to service ready mixed concrete

200.00
Northwest Europe marker price

160.00

US Central Appalachian coal spot price index Japan coking coal import cif price Japan steam coal import cif price

Price (US$/tonne)

120.00

80.00

40.00

0.00 1990 1994 Years 1998 2002 2006

Figure 1. Price changes of coal in different regions of the world. Source: British Petroleum, Statistical Review of World Energy 2008.

Figure 2: Teragrams of CO2 Equivalents Source: US EPA, 2006 US sources of CO2 emissions. Inventory of U.S. Greenhouse Gas Emissions and Sinks: 1990-200

Figure 3. 1996-2007 CCP Beneficial Use versus production. Source: American Coal Ash Association

Figure 4. World net Electricity generation by fuel, 2007-2035 (trillion kilowatt hours) Source, U. S Energy Administration 2010 CO2 forecast highlights

Figure 5.Construction of base for a heat treating facility in Houston, Texas. Cycling of temperatures caused severe breakdown of conventional concrete. Source: James K. Hicks, et al (2009).

Figure 6. Micrograph of CSH Formation in Activated Fly Ash Cement, Sample age is 14 months from addition of water Source: James K. Hicks, et. al. (2009).

Figure 7. Ternary phase diagram showing theoretical cement, CeraTech Cement design. Source: CeraTech, Inc.

Figure 8. Marine Corps Engineers training for fast track construction and repair prior to deployment. Marine Corps Base Concrete Installation Source: James K. Hicks, et al (2009).

Table 1. Performance characteristics of an activated pozzolan based cement repair material. All testing was performed with air cured specimens. Source: CeraTech, Inc.

Table 2. Characteristics of an activated pozzolan cement fast return to service ready mixed concrete. 1 Source, CeraTech, Inc.

Notes:
1. Strength development and working times can be adjusted by varying the cement ratio and by use of various proprietary activator admixtures. 2. Test results based on 846 lbs. of cement per cubic yard mix design and Fast Set Activator 3. Test results based on 564 lbs. of cement per cubic yard mix design and Fast Set Activator